Process and composition for water proofing substrates

ABSTRACT

A process and composition for water proofing materials which comprises treating a reactive or polar substrate with at least one reactive polyalkylene copolymer of the formula   AND CURING THE TREATED SUBSTRATE AT FROM 80*C. to 170*C. for from 0.1 minute to 3 hours; wherein C1 and C2 are carbon atoms in the main polyalkylene copolymer chain, R and R&#39;&#39; are hydrogen, alkyl, phenyl, -COOH or a segment of a polyalkylene chain and R1 and R2 are alkyl, aryl, aralkyl, alkaryl, or the like, of up to about 20 carbon atoms. The treatment in accordance with the present invention results in an improvement in the water repellent properties of the treated substrate, and, additionally, shrinkproofs those substrates which were subject to shrinkage.

United States Patent [191 Vaughn et al.

[ Jan. 14, 1975 1 PROCESS AND COMPOSITION FOR WATER PROOFING SUBSTRATES [75] Inventors: Walter L. Vaughn; Sherman Kottle;

Richard H. Symm, all of Lake Jackson, Tex.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: 'Apr. 12, 1974 [21] Appl. No.: 460,326

Related US. Application Data [60] Division of Ser. No. 218,009, Jan. 14, 1972, which is a continuation-in-part of Ser. No. 9,975, Feb. 9, 1970, abandoned.

UA, 89.5 S

[56] References Cited UNITED STATES PATENTS 2,849,426 8/1958 Miller 260/79.5 R 3,404,134 10/1968 Rees 260/78.5 T 3,441,545 4/1969 Blatz et al. 260/78.5 T 3,442,870 5/1969 Lohse et al.... 117/132 B 3,523,930 8/1970 Maloney 260/80.8 3,687,909 8/1972 Vaughn 260/80.78 3,787,366 1/1974 Vaughn 117/124 E FOREIGN PATENTS OR APPLICATIONS 1,024,388 3/1966 Great Britain Primary ExaminerWilliam D. Martin Assistant ExaminerJanyce A. Bell Attorney, Agent, or FirmWalter J. Lee

[5 7] ABSTRACT A process and composition for water proofing materials which comprises treating a reactive or polar substrate with at least one reactive polyalkylene copolymer of the formula and curing the treated substrate at from 80C. to 170C. for from 0.1 minute to 3 hours; wherein C, and C are carbon atoms in the main polyalkylene copolymer chain, R and R are hydrogen, alkyl, phenyl, -COOH or a segment of a polyalkylene chain and R and R are alkyl, aryl, aralkyl, alkaryl, or the like, of up to about 20 carbon atoms. The treatment in accordance with the present invention results in an improvement in the water repellent properties of the treated substrate, and, additionally, shrinkproofs those substrates which were subject to shrinkage.

7 Claims, N0 Drawings PROCESS AND COMPOSITION FOR WATER PROOFING SUBSTRATES CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisional of application Ser. No. 218,009 filed Jan. 14, 1972 which is a continuation-inpart of application Ser. No. 9,975 filed Feb. 9, 1970 and now abandoned.

BACKGROUND OF THE INVENTION The low molecular weight reactive polyalkylene copolymers (hereinafter called reactive polymers) taught herein are suitably applied from such closed loop solvent processes, and, when applied in accordance with the present invention, improve the water repellent properties of suitable substrates, as well as dimensionally stabilizing said substrates which are susceptible to shrinking.

SUMMARY OF THE INVENTION In accordance with the present invention, a suitable substrate is treated with one or more reactive polymers and cured at from about 80 to about 170C. for 0.1 minute to 3 hours, as necessary.

The reactive polymers which have been found to impart improved water repellent properties, as well as dimensional stability, to the treated substrate may be one or more polyalkylene copolymers containing groups of the formulas wherein C and C are, independently, carbon atoms in the main polyalkylene chain, R and R are, independently, hydrogen, alkyl groups of up to about 20 carbon atoms, phenyl, COOH or a segment of the polyalkylene chain, and R and R are, independently, alkyl, aryl, aralkyl, alkaryl, or the like, of up to about 20 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION Process The process of the instant invention may suitably be carried out in the following manner:

1. A reactive or polar substrate is treated with the composition of this invention in a number of wellknown ways, such as, for instance, dipping, padding, spraying and the like. It is suitable to treat the fiber with from about 5 to about 100 weight wet pick-up of the total composition, 40 to weight being preferred.

The composition is suitably an inert anhydrous solvent which contains from about 0.05 to about 20 weight (preferably 0.1 to 3 weight of one or more of the reactive polymers.

2. The excess solvent may then be removed by, for

instance, using heat and/or gaseous flow, or simultaneously removed during step (3) below.

3. The treated substrate is subjected to a thermal cure to cross-link the reactive polymer.

It is to be noted that positive pressures maybe utilized in (1) above to aid in impregnating the substrate with the polymer-laden solvent. For instance, pressures of up to about 150 p.s.i.a. may be utilized to assist in the impregnation of solid or particulate wood. Other uses of positive pressure for assisting in the impregnation of substrates, and of negative pressure to assist in the removal of excess solvent, will be apparent to those skilled in this art.

Those reactive or polar substrates which are amenable to the process and composition of this method include bulk wood, particulate wood, paper, starch, wood pulp, pressboard, and the like, as well as textile fibers such as cotton, wool, cotton-wool blends, cottonpolyester blends, wool-polyester blends, and other reactive or polar natural and synthetic substrates, and their blends, such as leather (natural and synthetic), fur (natural and synthetic), hair, jute, hemp, silk and the like.

The various natures of the above substrates require some variation in the process to achieve optimum results. The most desirable conditions for each type of substrate is outlined below:

1. Bulk wood and pressboard The substrate may be impregnated in any one of the above-mentioned ways; however, it is preferred to utilize positive pressure to improve and speed penetration. A wet pick-up of about 15 weight to saturation with a 0.1 to 15 weight polymer solution is generally suitable.

After removal of excess solvent by, for instance, the aforementioned techniques, the substrate is suitably subjected to cure conditions of about 80-l 50C. for at least about 30 minutes.

2. Paper, wood pulp, particulate wood, starch, etc.

These substrates may again be impregnated in any of the above ways. Pressure is not generally necessary, but may be utilized to assist impregnation, if desired. A wet pick-up of about 5 weight to saturation (preferably at least about 40 weight with a 0.5 to 10 weight polymer solution is generally suitable.

After removal of excess solvent the substrate is suitably subjected to cure conditions of about 80-170C. for about 0.1 to 60 minutes, as necessary.

3. Cotton, wool, blends, leather, fur, fibers generally,

etc.

These substrates may once again be impregnated in any of the above standard ways. Pressure considerations are the same as in 2 above. A wet pick-up of about 10 weight to weight (preferably 40 to 80 weight with a 0.3 to 10 weight (preferably 0.5 to 5 weight polymer solution is generally suitable for this application.

The cure conditions taught in 2 above also apply for these substrates. Solvents Solvents which are suitable in the method of this invention, as well as in the preparation of the polymeric compositions, as taught below, include chlorinated hydrocarbon solvents, such as l,l,l-trichloroethane, perchloroethylene, ethylene dichloride, methylene chloride, o-dichlorobenzene and the like; other organic solvents such as benzene, toluene, dioxane, xylene, heptane and higher aliphatics; alkyl acetates; tetrahydrofuran; fluorohalocarbons such as trichlorofluoromethane, trifluorotrichloroethane, dibromotetrafluoroethane, tetrachlorodifluoroethane and those fluorohalocarbons which are suitable for use herein for aerosol applications; and mixtures of the above. Preferred solvents include perchloroethylene and 1,1,1- trichloroethane and methylene chloride. Polymeric Compounds The polymeric compounds useful in the method and compositions of this invention include those of Formu las I or ll as defined above and their mixtures. Suitable are those polymers with molecular weights of from about 800 to those of high polymers, while 1,000 to about 6,000 is preferred.

The various precursor polymers utilized to prepare the polymeric compounds utilized herein are known to the art, generally being olefin/acid or olefin/acid halide polymers. They may be prepared according to a number of US. Pat. Nos. including 3,441,545, 3,310,518, 3,361,842 and 3,413,272.

They are typically prepared by polymerizing an alpha olefin, such as ethylene and/or propylene, with an alpha-, beta-ethylenically unsaturated carboxylic acid, in the presence of a catalyst and under superatomospheric pressure generally greater than about 10,000 psi. These polymers may then be modified to, for instance, acid halides, esters, amides and the like. They may be prepared from monomers which are well known in the art, including such compounds as alkenes and alkadienes, such as ethylene, propylene, butene, isobutene, pentene, hexene, octene, butadiene, isoprene, etc., (the term alkenes is intended to also include cycloalkenes, such as cyclohexene); unsaturated esters, such as acrylateand methacrylate-containing monomers, such as alkyl and cycloalkyl (1 to 20 carbon atoms) acrylates and methacrylates, such as methyl methacrylate, ethyl acrylate, t-butyl acrylate, 2- ethylhexyl methacrylate, cyclohexyl acrylate and the like; vinyl acetate, vinyl propionate, vinyl butyrate, dimethyl maleate, diethyl maleate, ethyl hydrogen maleate, monoethyl fumarate and diethyl fumarate; nitriles and amides containing unsaturated groups, such as acrylonitrile, methacrylonitrile, acrylamide and methacrylamide; olefinically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and cinnamic acid; and chlorinated and brominated derivatives of the above.

The reactive polymeric compounds, then, are prepared from the above precursors by different routes depending upon the nature of the reactive group, said groups being represented by Formulas l and II above. Each type will be discussed separately with respect to its preparation:

A. B-lactone-Containing Polymers of Formula I Polyalkylene copolymers containing interlinking beta-lactone groups of the formula are prepared by treating an olefin-alkylene carboxylic acid copolymer containing at least one group of the formula with a tertiary amine to interlink at least two segments of said copolymers through a beta-lactone group of Formula (I), wherein C and C are, independently, carbon atoms in the polyalkylene chain; R and R are, independently, hydrogen, alkyl groups of up to about 20 carbon atoms, phenyl, COOH or a segment of the polyalkylene chain and X is a halogen such as chlorine or bromine.

The precursor olefin-carboxylic acid copolymer may be derived as described above. There is the requirement, however, that the monomers used to prepare said precursor polymers contain at least about 4 to 5 weight percent based on total starting polymer of one or more monomers which will result in, or may be modified to, one or more groups pendant from, or terminal to, the polymer backbone, said groups being of Formula (lA) above.

Examples of said monomers include acrylic acid, itaconic acid, cinnamic acid and the acid halides thereof and crotonoic acid, 3-butenoic acid, 4-pentenoic acid, 3-hexenoic acid and the like and the acid halides thereof.

It is to be noted that C and C may be in a single polymer chain, thereby resulting in a cyclic polymer.

These copolymers, then may suitably be prepared by contacting about 0.005 to 20.0 weight (preferably 1.0 to 2.0 weight of the acid halide-containing polymer in a suitable inert solvent with agitation and under anhydrous conditions at no more than about 60C. (preferably 20 to 30C.), with a tertiary amine compound. The beta-lactone-containing polymer results.

Tertiary amines which are suitable include trialkyl and triaralkyl amines, such as trimethylamine, triethylamine, triisopropylamine, diethylmethylamine, ethylmethylpropylamine and tribenzylamine; tertiary cyclic amines, such as N-ethylpiperidine, N- isopropylpiperidine, N-methylhexahydroazepine, N- ethylpyrrolidine; and tertiary polyalkylenepolyamines, such as N,N-diethyl-N,N'-dimethylethylenediamine.

It is to be noted that the amount of residual acid halide groups desired on the beta-lactone-containing polymer, if any, will dictate the amount of tertiary amine to be utilized. If it is desired to lactonize all, or substantially all, the above groups, generally a slight excess over equivalency is to be utilized. Generally from about 1 to amine equivalents per acid halide equivalent are suitable, while 3 to 5 are preferred.

Pressure is not a critical variable in the lactonization process taught herein, and may suitably be super-, subor atmospheric pressures.

It is to be noted that these beta-lactone-containing polymers will generally cross-link in storage when the concentration of said polymer in solvent exceeds about 4 to 6 weight percent. However, the polymers may be made in concentrations of up to 20 weight percent and then diluted. Even if partial cross-linking occurs, the remaining reactive groups may be utilized as taught karyl, aralkyl or like groups of up to about 20 carbon atoms.

The precursor polyalkylene copolymer may, as in A, be derived as described above. However, in this case herein. Also, heating the solution above about 60C. 5 there is the requirement thatthe monomers used to for a period of time in excess of about one hour will prepare said precursor polymers contain at least one also result in coss-linking. Further, addition to the solu-' monomer group which will result in a group of Formula tion of a non-solvent (such as acetone, pentane and the (HA) above. Examples of said monomers include acrolike) may cause a loss of solubility of the polymer, lein, methacrolein, crotonaldehyde, cinnamaldehyde, thereby resulting in at least some cross-linking. tigaldehyde, a-methylisocrotonaldehyde, 3-butenal, The preferred reactive copolymers of Formula (I) in- 3 -m hy -2-buten l, fi-m hy ro n l hy e a the clude those which are derived by the above method llke) from precursor polymers of the general formula (desig- The betarlactonfi'com ammg P y F nating copolymerized i i AQH:S mph) B wt invention, then, may suitably be prepared t y reacting, C(5 25 wk We) D040 101%), A, B, C and D Suitably being in 5 at no more than about 60 C. (preferably to 30 C.), any order, wherein A is ethylene, B is propylene, C is to about 20 welght P (P f y 1 acrylic acid, and D is one of methyl acrylate, ethyl acrywelght of the CH0 groupcontammg Polymer m late, methyl methacrylate, ethyl methacryhte, a suitable solvent, with a keto-ketene of Formula (IIB) isobutylacrylate, acrylonitrile, or the like. More prefer- The betarlactonejcomaining Polymer ably, propylene i present at f 0 to about 1 weight 20 Suitable keto-ketenes include, for example diphenyl ketene, dimethyl ketene, ethylbutyl ketene, diethyl ke- For further details regarding this particular polymer, term y p pfl ketene, y p y ketene diiso' see copending application Ser. No. 1 1,361, entitled Propy] ketene dlbenzyl ketener phenylethyl k i Reactive Beta-Lactone-Containing Polymers and a ethylmethyl ketene, methylphenyl and the like- Method for Their Preparation," filed concurre tl It is to be noted that the amount of residual aldehyde herewith, now US. Pat. No. 3,687,909. groups desired on the beta-lactone-containing polymer, 3 L C m i i polymers f l if any, will dictate the amount of keto-ketene to be utip l lk l copolymers containing betaqacmne lized. If it is desired to lactonize all, or substantially all, groups f the f l the above groups, generally a slight excess over equiva- Iency is to be utilized. Generally from about 0.5 to about 5 keto-ketene equivalents per polymeric alde- R1 it hyde equivalent is suitable while 1 to 3 is preferred.

u (m Pressure is not a critical variable in the method of this 6 invention and may suitably be sub-, superor atmospheric.

T The same cautions regarding storage as were taught are prepared by treating a polyalkylene copolymer con- I in A pp y to this P taining at least one group of the formula Pfefel'red polyalkylene Precursor P y for Pf paring Formula II polymers are of the formula (desig- L 0 nating copolymerized moieties A B 0, (HA) C D A, B, C and D suitably being in any order, wherein A is ethylene, B is propylene, C is a with a keto-ketene of the formula monomer which will result in an aldehyde group of formula (IIA), and D is one or more unsaturated ester, r amide and/or nitrile as enumerated above, all %s being 0:0:0 ([15) weight of total. The more preferred copolymers of this invention include those which are prepared from the keto-ketenes, to form one or more beta-lactone groups of Formula specified herein, and the precursor polymers illustrated (II), wherein C is a carbon atom in the polyalkylene below. All %s are weight percent of total, and the legchain, and R and R are, independently, aryl, alkyl, alend for the symbols used follows the list:

1) E(4599%) P(040%) A (145%) 2) E (25-98%) do. do. VA 3) do. do. do. EA (do.) 4) do. do. do. MA (do.) 5) do. do. do. [BA (do.) 6) do. do. do. MMA (do.) 7) E(4S99%)- do M(ll5%) s) E(2598%)- do. dO. VA (1-20%) 9) do. do. do. EA (do.) 10) do. do. do. MA (do.) ll) do. do. -do. IBA (do.) 12) do. do. do. MMA (do.) 13) et30-99%) Cit), C(l-30%) l4) do. do CM (do.) l5) do. do T (do.)

E Ethylene MA Methyl Acrylate P Propylene lBA lsobutyl Aerylate A Acrolein MMA Methyl Methacrylatc M Methacrolein C Crotonaldehyde VA Vinyl Acetate CM Cinnamaldehyde EA Ethyl Acrylate T Tigaldehyde For further details regarding this particular reactive polymer, see copending application Ser. No. 11362, entitled Reactive Beta-Lactone-Containing Polymers and a Method for Their Preparation, filed concurrently herewith, now US. Pat. No. 3,787,366.

For application to textiles, fibers, and the like, such 10 as cotton, wool, blends, leather, fur, etc., it is preferred to use about 1.0 to about 5.0 weight of one or more polymers described above, most preferably about 1.0 to about 3.0 weight in perchloroethylene or 1,1,1-

trichloroethane.

Specific Embodiments EXAMPLE 1 Substrates were treated utilizing the process and compositions of this invention. The procedure was generally as follows:

A 1% by weight solution of the indicated polymer (legend below) in 1,1,l-trichloroethane was applied to the substrate by the indicated method. The add-on is the weight of polymeric material retained by the substrate after application and removal of the excess solvent. The treated substrates were then subjected to curing conditions, i.e., 120C. for the indicated time.

The results with respect to water repellency are carefully to insure uniformity of add-on. The fabric was allowed to air dry, and was then thermally cured in an oven at the specified temperature and time. The add-on is, once again, the weight of polymeric material rctained by the fabric.

Two results are given Shrinkage Reduction on some and Spray Rating on others.

A sample of about 8 inches to a side was prepared and a square 5 inches to a side ruled off within the interior of the sample. The sample was then labeled, washed and dried. The dimensions were again taken, and the following formula used to calculate area shrinkage:

[(Area of unwashed wool Area after washing) X IOO/Area of unwashed wool] Shrinkage Reduction is 100% minus the Area Shrinkage.

The Spray Test consisted of allowing a spray of water to fall onto the fabric, under controlled conditions, and

comparing the effect with a standard chart. The resistance of the fabric to surface wetting was measured, without accounting for penetration. The results are rated numerically from O to 100 for surface wetting as described below:

100 No sticking or wetting of the upper surface 90 Slight random sticking or wetting of upper surface shown below in Table I. 80 Wetting of upper surface at spray points TABLE 1 Ex. Polymer Weight Cure Time Treatment No. Type Substrate Add-on (min.) Method Results 1 A Yellow Pine (Pieces)* 0.2 15 Soaking Resisted wetting by H O beads for over 30 minutes 2 A Cellulose Powder 0.4 5 Wetting Floated on surface of H 0 several weeks without wetting 3 A Filter Paper 0.5 3 Wetting H O beads evaporated without any signs of wetting A Ethylene (60 wt, '70) Propylene (27 wt. Bcta-LactonePcndant (13 wt. '16). M.W, 3600 This example was repeated using white pine. l'ir. birch. and mahogany and the same results obtained.

EXAMPLE 2 A small swatch of wool fabric was placed in a flatbottomed glass container and a 10 ml. portion of about 1.5 weight of a polymer in 1,1,l-trichloroethane was added to the swatch by pipette. The addition was made 70 Partial wetting of whole or upper surface 50 Complete wetting of whole or upper surface 0 Complete wetting of whole or upper and lower surfaces The following Table 11 gives a representative example:

A Ethylene wt. propylene (27 wt. B-lactone (13 wt. 36), M.W. 36.00.

EXAMPLE 3 The following reactive lactone-containing polyalkylene copolymers were prepared and were found, employing substantially the same procedure described above, to impart water-resistant properties to paper and other reactive or polar substrates.

TABLE III REACTIVE lNTERPOLYMERS CONTAINING ETHYLENE/PROPYLENE/PENDANT B-LAC'lUNl-T Name of Reactive Derivative Description ethylene-propylene-methyl acrylate-B-lactone grease ethylene-propylene-ethyl acrylatefi lactone grease ethylene-propylene n-propyl acrylate-B-lactone grease ethylene-propylene'isopropyl acrylate-B-lactone grease ethylene-propylene-tert-butyl acrylate-fl-lactone grease ethylene-propylene-cyclohexyl acrylate-B-lactone grease ethylene-propylene-benzyl acrylate-B-lactone grease ethylene-l-heptyl acrylate-B-lactone grease ethylene-Z-octyl acrylate-B-lactone grease ethylene-propylene-tert-amyl acrylate-B-lactone grease ethylene-propylene-n-decyl acrylate-B-lactne grease ethylene-propylene-crotyl acrylate-B-lactone grease ethylene-propylene-myristyl acrylate-B-lactone grease ethylene-propylene-cetyl acrylate-B-lactone grease ethylene-propylene-acryl N-isopropylamide-B-lactone wax cthylene-propylenesorbitol acrylate-B-lact0ne grease cthylene-propylene-2-hydroxyethyl acrylate-B-lactone* grease ethylene-propylene-2,B-dihydroxypropyl acrylate-B-lactone* wax ethylene-propylene-bisphenol acrylate-B-lactone* wax ethylene-propylene-B-lactone-amide of cthylenediamine* wax ethylene-propylene-B-lactone -acrylate of dipropyleneglycol* wax ethylene-propylene-BJactone-acrylate of P-400* solid ethylenepropylene-B-lactone-acrylate of P-4000* solid ethylene-propylene-B-lactone-amide of PEI-6* solid ethylene-propylene-B-lactone-mixed amide and acrylate of N-ethyl cthanolamine* solid ethylene-propylene-B-lactone-mixed amide and acrylate of l,3-diaminopropanol-2* solid All products prepared in l% concentration in Chlorothene solution.

Partially crosslinkcd. insoluble or slightly soluble in chlorinated and other organic solvents.

EXAMPLE 4 Lactones prepared by the action of keto-ketenes on low molecular weight polyalkylene copolymers containing pendant CHO groups are dissolved in suitable solvents and employed, in substantially the same manner as in Examples 1 and 2, to impart water-resistance to paper and other reactive or polar substrates.

Of special interest as precursor polymers are polyalkylene copolymers prepared by copolymerizing a major amount of ethylene with a minor amount of acrolein or methacrolein.

We claim:

1. A process for improving the dimensional stability or water repellency of reactive or polar substrates which comprises treating the substrate with from 5 to 100 weight wet pick-up of treating composition, and curing the treated substrate at from about 80C to about 170C for about 0.1 minute to about 3 hours wherein the said treating composition comprises an inert anhydrous solvent containing from about 0.05 to about weight percent of one or more reactive polyalkylene copolymers of the formulas 6. The process of claim 1 wherein the polyalkylene copolymer is one designated by the formula 7. The process of claim 1 wherein the concentration of the polyalkylene copolymer in the inert anhydrous solvent is in the range of from about 0.1 to about 3 weight percent.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,860,441 D ED I January 14, 1975 |NVENT0R(5) 1 Walter L. Vaughn, Sherman Kottle, Richard H. Symm It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 25-26, enclose the expression closed loop within quotations marks.

Col. 4, line 34, after "4-pentanoic acid,", insert 3-pentenoic acid, S-hexenoic acid, 4hexenoic acid,

Col. 7, line 6, after "and", insert the Col. 8, bottom line below Table II, correct "36.00" to Signed and Scaled this seventh Day of Oct0 ber1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'larenls and Trademarks 

1. A PROCESS FOR IMPROVING THE DIMENSIONED STABILITY OR WATER REPELLENCY OF REACTIVE OR POLAR SUBSTRATES WHICH COMPRISES TREATING THE SUBSTRATE WITH FROM 5 TO 100 WEIGHT % WET PICK-UP OF TREATING COMPOSITION, AND CURING THE TREATED SUBSTRATE AT FROM ABOUT 80*C TO ABOUT 170*C FOR ABOUT 0.1 MINUTE TO ABOUT 3 HOURS WHEREIN THE SAID TREATING COMPOSITION COMPRISES AN INERT ANHYDROUS SOLVENT CONTAINING FROM ABOUT 0.05 TO ABOUT 20 WEIGHT PERCENT OF ONE OR MORE REACTIVE POLYALKYLENE COPOLYMERS OF THE FORMULAS
 2. The process of claim 1 wherein the wet pick-up is from 40 to 80 weight percent.
 3. The process of claim 1 wherein positive pressure is utilized to assist in the application of the polymeric material to the substrate.
 4. A substrate with improved water repellency as produced by the process of claim
 1. 5. The process of claim 1 wherein the polyalkylene copolymer is one designated by the formula
 6. The process of claim 1 wherein the polyalkylene copolymer is one designated by the formula
 7. The process of claim 1 wherein the concentration of the polyalkylene copolymer in the inert anhydrous solvent is in the range of from about 0.1 to about 3 weight percent. 